The Chemistry of Organo Halogenic Molecules. 155. The Role of Reagent Structure in Halogenation of 9-Substituted Phenanthrenes

9-Substituted phenanthrenes were used as target molecules in investigations of the effect of the reagent structure and reaction conditions on halogenation with bromine (1), CsSO4F (2) and F-TEDA (1-chloromethyl-4-fluoro-1,4-diazoniabicycloe[2,2,2]octane bis(tetra- fluoroborate), (3). 9-Methoxyphenanthrene (4) was converted to 9- bromo-10-methoxyphenanthrene (6a) and 9-bromo-10-hydroxy- phenanthrene (7a), while the amount of dealkylation depended on the solvent and was more pronounced in methanol than in acetonitrile, but no adduct was observed. Addition reaction became a major process in fluorination with CsS04F (2) in methanol and 88% of 9-fluoro-10,10-dimethoxy-9,10-dihydrophenanthrene (8b) was formed, while dealkylation occurred in acetonitrile. The course of fluorination of 9-methoxyphenanthrene with F-TEDA (3) could be completely manipulated by the choice of solvent and 9,9-difluoro- 10-oxo-9,10-dihydrophenanthrene (9b) was formed in acetonitrile, 9-fluoro-10-methoxyphenanthrene (6b) in trifluoroacetic acid and 9-fluoro-10,10-dimethoxy-9,10-dihydrophenanthrene (8b) in methanol. Bromination of 9-hydroxyphenanthrene (5) in acetonitrile resulted only in the substitution process, while 9-fluoro-10-hydroxyphenanthrene (7b) formed in the reaction with CsSO4F and F-TEDA was more reactive than the starting hydroxy derivative and, using a 2 molar ratio of F-TEDA, only 9,9-difluoro-10-oxo- 9,10-dihydrophenanthrene (9b) was formed